((methyl)(Cl)Si(η5-C5Me4)(η1-N(t)Bu))TiCl2 | 633346-40-4

• 英文名称: ((methyl)(Cl)Si(η5-C5Me4)(η1-N(t)Bu))TiCl2
• 英文别名: [Ti(η5-C5Me4SiMeCl-η1-N-t-Bu)Cl2]
• CAS: 633346-40-4
• 化学式: C₁₄H₂₄Cl₃NSiTi
• 分子量: 388.676
• InChiKey: SWESCUICQSOGPU-NMRXSTGRSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [Ti(η5-C5Me4SiMeCl2)Cl3] 、 lithium tert-butylamide 以 乙醚 为溶剂， 以41%的产率得到((methyl)(Cl)Si(η5-C5Me4)(η1-N(t)Bu))TiCl2
  参考文献：
  名称：

  加氢和氯取代的甲硅烷基和甲硅烷基的η 1 -酰氨基-η 5 -四甲基环戊钛络合物

  摘要：

  氯甲硅烷基环戊二烯钛前体钛[Ti（η 5 -C 5我4 SiMeXCl）氯3 ]（X = H 2，氯3）通过的TiCl反应制备4与相应的环戊二烯的三甲基甲硅烷衍生物。得到甲基络合物的这些化合物与MgClMe适当条件下的甲基化钛[Ti（η 5 -C 5我4森达2 R）XME 2 ]（R = H，X =氯5中，Me 6 ; R = X =我7） 。的反应2和3与灵两个当量吨卜得到柄-甲硅烷-η-酰胺化合物钛[Ti {η 5 -C 5我4 SIMEX（η 1 -N吨丁基）}氯2 ]（X = H 8，氯9）。的甲基化8，得到钛[Ti {η 5 -C 5我4 SiMeH（η 1 -N吨丁基）}我2 ] 10。配合物8也可以通过8与BCl 3的反应获得，而相同的反应是使用氯化剂（TiCl 4，盐酸盐）导致脱酰胺，得到2，将其也被转换成3与Bcl由反应3。所有这些新化合物都通过NMR光谱进行了表征，并通过X射线衍射法确定了2和4的分子结构。

  DOI：

  10.1016/s0022-328x(03)00559-x

文献信息

• Silylium–metallocenium dications derived from hydrosilyl-bridged metallocenes and roles in polymerization of polar and nonpolar vinyl monomers
  作者：Yuetao Zhang、Eugene Y.-X. Chen

  DOI：10.1016/j.jorganchem.2010.02.030

  日期：2010.5

  Hydrosilyl-bridged half-metallocene ((H)CGC)TiMe2 (1) [(H)CGC = Me(H)Si(eta(5)-C5Me4)(eta(1)-(NBu)-Bu-t)] and ansa-metallocene rac-((SBI)-S-H)ZrMe2 (2) [(SBI)-S-H = Me(H)Si(eta(5)-indenyl)(2)] are doubly activated with 2 equiv of Al(C6F5)(3), through methide abstractions from both M-Me bonds, to generate homo-dications 1-Ti2+ and 2-Zr2+, or with 2 equiv of Ph3CB(C6F5)(4), through unique simultaneous hydride and methide abstractions from the Si-H and M-Me bonds, to produce a novel class of silylium-metallocenium hetero-dications 1-Si+Ti+ and 2-Si+Zr+. Analogous chloride-derivatives of hetero-dications can also be produced starting from the dichloride precursors, but the chloride abstraction occurs through a transit silylium ion. An opposite activity trend has been observed for the influence of the hetero-dication formation on polymerizations of polar (MMA) and nonpolar (propylene) vinyl monomers. In MMA polymerization, the activity of the hetero-dications, especially the metallocene-based 2-Si+Zr+, is substantially lower than the corresponding monocations. In marked contrast, the propylene polymerization activity of hetero-dications has seen 100% and 40% enhancements for 1-Si+Ti+ and 2-Si+Zr+, respectively, over their respective monocations. (C) 2010 Elsevier B.V. All rights reserved.